CN114927659A - Multi-element anode material and preparation method and application thereof - Google Patents
Multi-element anode material and preparation method and application thereof Download PDFInfo
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- CN114927659A CN114927659A CN202210492025.2A CN202210492025A CN114927659A CN 114927659 A CN114927659 A CN 114927659A CN 202210492025 A CN202210492025 A CN 202210492025A CN 114927659 A CN114927659 A CN 114927659A
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- 239000010405 anode material Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title abstract description 44
- 239000002245 particle Substances 0.000 claims abstract description 210
- 239000013078 crystal Substances 0.000 claims abstract description 138
- 239000007774 positive electrode material Substances 0.000 claims abstract description 67
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 11
- 239000010406 cathode material Substances 0.000 claims description 59
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 45
- 239000011572 manganese Substances 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 29
- 239000002243 precursor Substances 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 229910052782 aluminium Inorganic materials 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 22
- 229910052750 molybdenum Inorganic materials 0.000 claims description 20
- 238000005245 sintering Methods 0.000 claims description 20
- 229910052719 titanium Inorganic materials 0.000 claims description 20
- 229910052721 tungsten Inorganic materials 0.000 claims description 20
- 229910052726 zirconium Inorganic materials 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 18
- 238000012360 testing method Methods 0.000 claims description 18
- 229910052796 boron Inorganic materials 0.000 claims description 17
- 229910052758 niobium Inorganic materials 0.000 claims description 16
- 229910052720 vanadium Inorganic materials 0.000 claims description 16
- 239000011248 coating agent Substances 0.000 claims description 15
- 239000002019 doping agent Substances 0.000 claims description 13
- 229910003002 lithium salt Inorganic materials 0.000 claims description 13
- 159000000002 lithium salts Chemical class 0.000 claims description 13
- 239000008139 complexing agent Substances 0.000 claims description 12
- 229910052804 chromium Inorganic materials 0.000 claims description 10
- 150000001868 cobalt Chemical class 0.000 claims description 10
- 229910052746 lanthanum Inorganic materials 0.000 claims description 10
- 150000002696 manganese Chemical class 0.000 claims description 10
- 150000002815 nickel Chemical class 0.000 claims description 10
- 238000012216 screening Methods 0.000 claims description 10
- 229910052727 yttrium Inorganic materials 0.000 claims description 10
- 229910052788 barium Inorganic materials 0.000 claims description 8
- 229910052749 magnesium Inorganic materials 0.000 claims description 8
- 229910052712 strontium Inorganic materials 0.000 claims description 8
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- 239000000463 material Substances 0.000 abstract description 39
- 238000005056 compaction Methods 0.000 abstract description 14
- 230000000052 comparative effect Effects 0.000 description 23
- 239000000047 product Substances 0.000 description 13
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- 238000007599 discharging Methods 0.000 description 12
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- 229910052759 nickel Inorganic materials 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
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- 230000007547 defect Effects 0.000 description 7
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- 239000010941 cobalt Substances 0.000 description 6
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- 238000010438 heat treatment Methods 0.000 description 6
- 238000007086 side reaction Methods 0.000 description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
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- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
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- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 4
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- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
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- 239000002002 slurry Substances 0.000 description 4
- 229910018626 Al(OH) Inorganic materials 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
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- 229910021193 La 2 O 3 Inorganic materials 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
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- 235000019270 ammonium chloride Nutrition 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 238000010923 batch production Methods 0.000 description 2
- 229940011182 cobalt acetate Drugs 0.000 description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 2
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- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 2
- 229910001947 lithium oxide Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
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- 235000002867 manganese chloride Nutrition 0.000 description 2
- 229940099607 manganese chloride Drugs 0.000 description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
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- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
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- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the technical field of lithium ion battery anode materials, and discloses a multi-element anode material and a preparation method and application thereof. The multi-element positive electrode material comprises single crystal particles A and polycrystalline particles B; wherein the single crystal particles A have a median particle diameter D 50(A) 2-6 μm; the median diameter D of the polycrystalline particles B 50(B) 2-6 μm; the weight ratio of the single crystal grains A to the polycrystalline grains B is 1:9-9: 1. The multi-element anode material comprises single crystal particles A with small particle size and polycrystalline particles B with small particle size, wherein the single crystal particles A and the polycrystalline particles B have equivalent particle sizes, and the single crystal particles A and the polycrystalline particles B can realize advantage complementation, so that the multi-element anode material formed by matching the two particles not only keeps the high pole piece compaction density of the single crystal material, and has the advantages of stable structure, excellent cycle performance and good safety, but also has the advantages of high capacity and good power output of the small-particle polycrystalline material.
Description
Technical Field
The invention relates to the technical field of lithium ion battery anode materials, in particular to a multi-element anode material and a preparation method and application thereof.
Background
At present, the lithium ion battery industry develops rapidly, and along with the development of electronic products, the market also puts higher demands on lithium ion power batteries, especially considering the energy density, large-current discharge and safety performance, and in addition, the cost is low. Lithium cobaltate positive electrode materials are widely used as power sources for electronic cigarettes, electronic models, toys, wireless electric tools and small electric appliances because of high gram capacity and compaction density, excellent cycle performance, and particularly high discharge capacity and high platform during high-rate discharge. However, the cobalt resource is a scarce resource, the price of the cobalt resource is always high, and the cost advantage is not obvious.
For the existing power type anode material, the compressive strength is improved, the power output is improved, the safety performance of the material is ensured, the important direction for the development is provided, and the significance for improving the performance of the nickel cobalt lithium manganate ternary lithium ion battery is also realized.
CN109888235A discloses a graded high-nickel ternary positive electrode material, a preparation method and application thereof. The high nickel ternary cathode material with the gradation is prepared by mixing a high nickel polycrystalline material and a ternary single crystal material, or mixing the mixture with a coating additive and then sintering. The prepared grading material has higher compaction and cycle stability than a single polycrystalline material, has higher capacity than a single crystal, and can effectively improve the problems of gas generation and service life of a battery after grading modification. However, the polycrystalline material is large in particle and poor in compression resistance, the pole piece can crack after being rolled, the long-term circulation stability is poor, and the large particle power performance is poor.
Disclosure of Invention
The invention aims to solve the problems of poor power performance of a single crystal anode material and low mechanical strength, poor thermal stability and poor cycle performance of a polycrystalline anode material in the prior art, and provides a multi-element anode material and a preparation method and application thereof. The multi-element anode material comprises single crystal particles A with small particle size and polycrystalline particles B with small particle size, wherein the single crystal particles A and the polycrystalline particles B have equivalent particle sizes, and the single crystal particles A and the polycrystalline particles B can realize advantage complementation, so that the multi-element anode material formed by matching the two particles not only keeps the high pole piece compaction density, stable structure, excellent cycle performance and good safety of the single crystal material, but also has the advantages of high capacity and good power output of the small-particle polycrystalline material.
In order to achieve the above object, a first aspect of the present invention provides a multi-component positive electrode material, characterized in that the multi-component positive electrode material includes single crystal particles a and polycrystalline particles B;
wherein the single crystal particles A have a median particle diameter D 50(A) 2-6 μm; the median diameter D of the polycrystalline particles B 50(B) 2-6 μm;
the weight ratio of the single crystal grains A to the polycrystalline grains B is 1:9-9: 1.
A second aspect of the present invention provides a method for preparing the above multi-element positive electrode material, wherein the method comprises:
and mixing the single crystal particles A with the polycrystalline particles B to obtain the multi-element anode material.
The third aspect of the invention provides an application of the above multi-element cathode material in a lithium ion battery.
By the technical scheme, the multi-element cathode material and the preparation method and application thereof provided by the invention have the following beneficial effects:
(1) the multi-element anode material contains single crystal particles A and polycrystalline particles B, the advantages of the single crystal particles A and the polycrystalline particles B are complementary, and the median diameter D of the single crystal particles A 50 (A) With the median diameter D of the polycrystalline particles B 50 (B) In particular, the difference between the median particle diameters is within 1 μm. The single crystal particle A positive electrode material has high mechanical strength, provides particle support after mixing, can inhibit polycrystalline particles from being crushed, reduces side reaction with electrolyte, and has stable material structure and good cycle performance and safety; the single crystal material has good compression resistance, and the pole piece compaction density can be improved, so that the capacity is ensured; the positive electrode material of the polycrystalline particle B is small-particle polycrystalline particles, and larger-particle polycrystalline particles and single crystal particles have excellent rate capability and powerThe output is good, the particles with two structures are matched with each other, so that the high pole piece compaction density, the stable structure, the excellent cycle performance and the good safety of the single crystal material are maintained, and the advantages of high capacity and good power output of the small-particle polycrystalline material are also taken into consideration;
(2) the Ni content of the single crystal grain A is higher than that of the polycrystalline grain B, so that the charge-discharge depth and the discharge capacity of the single crystal A are not lower than those of the polycrystalline B under low current. Under the condition of large current, the discharge capacity of the polycrystal is high, the internal impedance of the polycrystal causes heating, and the polycrystal can be heated to activate the monocrystal, so that more lithium ions can be removed, higher capacity can be exerted, and the defect of low single crystal capacity can be overcome.
(3) The performance of the multi-element anode material has the characteristic of adjustability, and according to the application requirements of products, the single crystal particles A and the polycrystalline particles B can be mixed in different proportions, so that the power performance of the material and the like are exerted to the maximum extent, and the rapid charge and discharge requirements of the material are met;
(4) in the method for preparing the multielement cathode material, the coating additive is adopted, so that the defects on the surface of the cathode material can be repaired, the residual alkali amount on the surface is controlled, the stability of the structure is enhanced, the side reaction of the multielement cathode material and the electrolyte is reduced, the gas yield is reduced, and the safety of the battery is improved. The synergistic effect of the multi-element anode material and the doping additive can further improve the structural stability, the cycle performance and the power performance of the multi-element anode material, and the method has strong controllability, low cost and convenient batch production.
Drawings
FIG. 1 is an SEM photograph of a precursor of a single-crystal positive electrode material A obtained in example 1;
fig. 2 is an SEM image of a precursor of polycrystalline positive electrode material B prepared in example 1;
FIG. 3 is an SEM photograph of single-crystal particles A obtained in example 1;
FIG. 4 is an SEM photograph of polycrystalline particles B obtained in example 1;
FIG. 5 is an SEM image of a multi-element cathode material prepared in example 1;
fig. 6 is a graph of cycle performance at 1C rate for the multi-element positive electrode materials prepared in example 1 and comparative examples 1-2, where the test temperature is 45 ℃ and the voltage range is 3-4.3V.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a multi-element cathode material, which is characterized by comprising single crystal particles A and polycrystalline particles B;
wherein the single crystal particles A have a median particle diameter D 50(A) Is 2-6 μm; the median diameter D of the polycrystalline particles B 50(B) Is 2-6 μm;
the weight ratio of the single crystal grains A to the polycrystalline grains B is 1:9-9: 1.
In the present invention, the multi-component positive electrode material of the present invention contains both single crystal grains a of small particle size and polycrystalline grains B of small particle size, and the median particle size D of the single crystal grains a 50(A) With the median diameter D of the polycrystalline particles B 50(B) And the advantages of the positive plate and the negative plate are complementary, so that the multi-element positive electrode material has a stable structure, and the positive plate prepared from the multi-element positive electrode material has high compaction density, so that the lithium ion battery containing the multi-element positive electrode material has more excellent cycle performance and safety performance, and also has high battery capacity and excellent power output performance.
Specifically, the single crystal particle A positive electrode material is high in mechanical strength, provides particle support after being mixed, can inhibit polycrystalline particles from being broken, reduces side reaction with electrolyte, and is stable in material structure and good in cycle performance and safety; the single crystal material has good compression resistance, and the pole piece compaction density can be improved, so that the capacity is ensured; the positive electrode material of the polycrystalline particle B is small-particle polycrystalline particles, the multiplying power performance of larger-particle polycrystalline particles and single crystal particles is excellent, the power output is good, the mutual matching of the two structural particles not only maintains the high pole piece compaction density of the single crystal material, but also has the advantages of stable structure, excellent cycle performance and good safety, and simultaneously, the high capacity and the good power output of the small-particle polycrystalline material are considered.
Further, the median diameter D of the single crystal particles A 50(A) Is 3-5 μm.
Further, the median diameter D of the polycrystalline particles B 50(B) Is 3-5 μm.
Further, the weight ratio of the single crystal grains a to the polycrystalline grains B is 2:8 to 8: 2.
According to the invention, the median particle diameter D of the multi-element anode material 50 Is 2-6 μm.
In the invention, when the median particle diameter of the multi-element cathode material provided by the invention meets the range, the multi-element cathode material has good rate performance.
Further, the median diameter D of the multielement cathode material 50 Is 3-5 μm.
According to the invention, the median diameter D of the single-crystal particles A 50(A) And a median diameter D of the polycrystalline particles B 50(B) The absolute value of the difference is 1 μm or less.
According to the invention, when the absolute value of the difference between the median particle diameters of the single crystal particles A and the polycrystalline particles B is controlled to meet the range, the mechanical strength of the multi-element anode material can be further improved, the side reaction between the multi-element anode material and an electrolyte is reduced, the structural stability of the multi-element anode material is improved, and the excellent compression resistance of the multi-element anode material is ensured, so that an anode piece prepared from the multi-element anode material has high compaction density, and further a lithium ion battery containing the multi-element anode material has more excellent cycle performance and safety performance, and has high battery capacity, excellent power output performance and rate capability.
Further, the median diameter D of the single crystal particles A 50(A) And a median diameter D of the polycrystalline particles B 50(B) The absolute value of the difference is 0.8 μm or less.
According to the invention, the specific surface area of the monocrystalline particles AS A Is 0.4-1m 2 /g。
In the present invention, when the specific surface area of the single crystal particle a satisfies the above range, the single crystal particle has a moderate size, and can exhibit a high discharge capacity and also have a good structural stability.
Further, the specific surface area S of the single crystal particle A A Is 0.5-0.9m 2 /g。
According to the invention, the specific surface area S of the polycrystalline particles B B Is 0.9-2m 2 /g。
In the present invention, when the specific surface area of the polycrystalline particle B satisfies the above range, the polycrystalline particle has a good rate capability and a stable structure.
Further, the specific surface area S of the polycrystalline particles B B Is 1.1-1.6m 2 /g。
According to the invention, the monocrystalline particles A have a composition represented by formula I:
Li 1+a1 (Ni x1 Co y1 Mn z1 M 1m1 )J 1j1 O 2 formula I;
wherein-0.1. ltoreq. a 1 ≤0.1，0＜x 1 ＜1，0＜y 1 ≤0.4，0＜z 1 ≤0.6，0≤m 1 ≤0.1，0≤j 1 ≤0.02；M 1 At least one element selected from Ta, Cr, Mo, W, La, Al, Y, Ti, Zr, V, Nb, Ce, Er, Mg, Sr, Ba and B; j. the design is a square 1 At least one element selected from the group consisting of W, Mo, Zr, Al, V, Ti, B, Co and Nb.
Further, 0.01. ltoreq. a 1 ≤0.08，0.3＜x 1 ＜1，0.01＜y 1 ≤0.3，0.01＜z 1 ≤0.5，0≤m 1 ≤0.05，0≤j 1 ≤0.015；M 1 At least one element selected from the group consisting of Cr, Mo, W, La, Al, Y, Ti and Zr; j. the design is a square 1 At least one element selected from W, Mo, Zr, Al and Ti.
According to the invention, the polycrystalline grains B have a composition represented by formula II:
Li 1+a2 (Ni x2 Co y2 Mn z2 M 2m2 )J 2j2 O 2 formula II;
wherein-0.1. ltoreq. a 2 ≤0.1，0＜x 2 ＜1，0＜y 2 ≤0.4，0＜z 2 ≤0.6，0≤m 2 ≤0.1，0≤j 2 ≤0.02；M 2 At least one element selected from Ta, Cr, Mo, W, La, Al, Y, Ti, Zr, V, Nb, Ce, Er, Mg, Sr, Ba and B; j is a unit of 2 At least one element selected from W, Mo, Zr, Al, V, Ti, B, Co and Nb.
Further, 0.01. ltoreq. a 2 ≤0.08，0.3＜x 2 ＜1，0.01＜y 2 ≤0.3，0.01＜z 2 ≤0.5，0≤m 2 ≤0.05，0≤j 2 ≤0.015；M 2 At least one element selected from the group consisting of Cr, Mo, W, La, Al, Y, Ti and Zr; j. the design is a square 2 At least one element selected from W, Mo, Zr, Al and Ti.
According to the invention, x 1 ＞x 2 。
In the present invention, the Ni content in the single crystal grains A is controlled to be higher than that in the polycrystalline grains B, i.e., x 1 ＞x 2 And the charge-discharge depth and discharge capacity of the single crystal particles A under low current can be ensured to be not lower than those of the polycrystalline particles B. Under the condition of large current, the discharge capacity of polycrystalline particles is high, and the internal impedance of the polycrystalline particles causes heating, so that the single crystal particles can be heated, and the single crystal particles are activated, more lithium ions are removed, the higher capacity is exerted, and the defect of low capacity of the single crystal particles is overcome.
Further, x 1 -x 2 Is 0.01 to 0.1, more preferably 0.01 to 0.05.
According to the invention, the specific surface area of the multi-element cathode material is S 0 After 4.5T of pressure fracturing, the specific surface area of the multielement positive electrode material is S 1 ；
Wherein (S) 1 -S 0 )/S 0 *100％≤200％。
In the invention, when the specific surface area of the multi-element anode material before and after pressure fracturing meets the range, the mechanical strength of the material is higher, and the anode material is not easy to fracture in the manufacturing process of the pole piece, thereby keeping the material to have good electrochemical performance.
Further, (S) 1 -S 0 )/S 0 100% is 10-150%.
According to the invention, the granularity D corresponding to 5% of volume distribution obtained by granularity test of the multi-element anode material is 5 0 After 4.5T pressure fracturing, the granularity D corresponding to 5% of volume distribution obtained by granularity test of the multi-element anode material 5 1 ；
Wherein (D) 5 0 -D 5 1 )/D 5 0 X 100% is 1-30%.
In the invention, when the granularity corresponding to 5% of the volume distribution of the multi-element anode material before and after pressure fracturing meets the range, the anode material has higher mechanical strength, the anode material is not easy to fracture in the manufacturing process of the pole piece, and fine powder is not easy to generate under strong pressure, thereby keeping the material to have good processing performance and electrochemical performance.
Further, (D) 5 0 -D 5 1 )/D 5 0 X 100% is 1-25%.
According to the invention, the performance of the multi-element anode material has the characteristic of adjustability and controllability, and the single crystal particles A and the polycrystalline particles B can be mixed in different proportions according to the application requirements of products, so that the power performance of the material is exerted to the maximum extent, and the like, and the rapid charge and discharge requirements of the material are met.
In one embodiment of the present invention, when the weight ratio of the single crystal grains a to the polycrystalline grains B is 1.1 to 9:1, the multi-component positive electrode material satisfies at least one of the following conditions:
(i)0.5≤S 0 ≤1.2m 2 /g；
(ii)(S 1 -S 0 )/S 0 ×100％≤120％；
(iii)(D 5 0 -D 5 1 )/D 5 0 x 100% is 1-15%;
(iv)0≤(S 0 -S A )/S A ×100％≤50％；
wherein S is A Is the specific surface area of the single crystal particle A.
In the present invention, when the weight ratio of the single crystal grains a to the polycrystalline grains B in the multi-component positive electrode material satisfies the above range, that is, when the content of the single crystal grains a in the multi-component positive electrode material is greater than that of the polycrystalline grains B and the multi-component positive electrode material satisfies at least one of the above conditions, the multi-component positive electrode material has a stable structure and is excellent in cycle performance and thermal stability.
Further, the multielement cathode material satisfies at least one of the following conditions:
(i)0.5≤S 0 ≤1m 2 /g；
(ii)(S 1 -S 0 )/S 0 x 100% is 10-100%;
(iii)(D 5 0 -D 5 1 )/D 5 0 x 100% is 1-10%;
(iv)0≤(S 0 -S A )/S A ×100％≤30％；
wherein S is A Is the specific surface area of the single crystal particle A.
In one embodiment of the present invention, when the weight ratio of the single crystal grains a to the polycrystalline grains B satisfies 1:1.1 to 9, the multi-component positive electrode material satisfies at least one of the following conditions:
(1)0.8≤S 0 ≤1.4m 2 /g；
(ii)(S 1 -S 0 )/S 0 ×100％≤200％；
(iii)(D 5 0 -D 5 1 )/D 5 0 x 100% is 10-30%;
(iv)0≤(S B -S 0 )/S B ×100％≤50％；
wherein S is B Is the specific surface area of the polycrystalline particles B.
In the present invention, when the weight ratio of the single crystal particles a to the polycrystalline particles B in the multi-component positive electrode material satisfies the above range, that is, when the content of the polycrystalline particles B in the multi-component positive electrode material is greater than that of the single crystal particles a and the multi-component positive electrode material satisfies at least one of the above conditions, the multi-component positive electrode material has good rate capability.
Further, the multi-element cathode material satisfies at least one of the following conditions:
(1)1≤S 0 ≤1.3m 2 /g；
(ii)(S 1 -S 0 )/S 0 x 100% is 90-180%;
(iii)(D 5 0 -D 5 1 )/D 5 0 x 100% is 10-25%;
(iv)0≤(S B -S 0 )/S B ×100％≤30％；
wherein S is B Is the specific surface area of the polycrystalline particles B.
In a second aspect of the present invention, there is provided a method for preparing the above multi-element positive electrode material, the method comprising:
and mixing the single crystal particles A with the polycrystalline particles B to obtain the multi-element anode material.
In the present invention, the sources of the single crystal grains a and the polycrystalline grains B are not particularly limited, and may be commercially available or self-made.
In order to further ensure that the multielement cathode material has excellent electrochemical properties, preferably, the single crystal particles A and the polycrystalline particles B are prepared according to the preparation method provided by the invention. As long as it is ensured that the median particle diameters of the single crystal grains a and the polycrystalline grains B satisfy the requirements of the present invention.
Single crystal particle A
According to the invention, the monocrystalline particles A are prepared according to the following steps:
s1, mixing nickel salt, cobalt salt, manganese salt, a first precipitator and a first complexing agent in the presence of a solvent, adding the mixture into a reaction kettle to perform a first continuous reaction, and performing filter pressing, washing and drying to obtain a precursor of the single crystal anode material A;
s2, mixing the precursor of the single crystal anode material A with a first lithium salt and a first doping agent M 1 Mixing, and sinteringCrushing and screening to obtain a process product of the single crystal cathode material A;
s3, mixing the single crystal anode material A process product with the first coating agent J 1 Carrying out second sintering to obtain the single crystal particles A;
wherein M is 1 At least one element selected from Ta, Cr, Mo, W, La, Al, Y, Ti, Zr, V, Nb, Ce, Er, Mg, Sr, Ba and B, J 1 At least one element selected from W, Mo, Zr, Al, V, Ti, B, Co and Nb.
According to the preparation method provided by the invention, the single crystal particle A is prepared, and the process product of the single crystal anode material A is coated by the first coating agent, so that the defects on the surface of the anode material can be repaired, the surface residual alkali amount is controlled, the structural stability is enhanced, the side reaction of the multi-element anode material and the electrolyte is reduced, the gas generation rate is reduced, the battery safety is improved, and the first coating agent can be cooperated with the first doping agent introduced in the process product preparation process of the anode material, so that the structural stability, the cycle performance and the power performance of the multi-element anode material are further improved.
Furthermore, the preparation method of the single crystal particle A provided by the invention has strong controllability and low cost, and is convenient for batch production.
In some embodiments of the invention, the first lithium salt is used in an amount satisfying 0.9 ≦ n (Li)/[ n (Ni) + n (Co) + n (Mn) ] ≦ 1.1, and more preferably, the first lithium salt is used in an amount satisfying 1.01 ≦ n (Li)/[ n (Ni) + n (Co) + n (Mn) ] ≦ 1.08.
In some embodiments of the present invention, in order to obtain the precursor of the single crystal cathode material a, preferably, in step S1, the first continuous reaction is performed under the reaction conditions including: the temperature is 40-80 ℃, the time is 5-40h, the rotating speed is 300-900rpm, and the pH value is 10-13.
In some embodiments of the present invention, preferably, the median particle diameter D of the precursor of the single crystal positive electrode material a is smaller than the median particle diameter D of the precursor of the single crystal positive electrode material a 50 2-6 μm, and 5-25m of specific surface area 2 /g。
In some embodiments of the present invention, preferably, in step S2, the first sintering is performed in an air or oxygen atmosphere, and the conditions of the first sintering include: the temperature is 600 ℃ and 1100 ℃, and the time is 6-30 h.
In some embodiments of the present invention, preferably, in step S3, the second sintering is performed in an air or oxygen atmosphere, and the conditions of the second sintering include: the temperature is 200 ℃ and 900 ℃ and the time is 6-30 h.
In some embodiments of the present invention, preferably, in step S1, the nickel salt, the cobalt salt, and the manganese salt are each independently selected from at least one of sulfate, chloride, nitrate, and acetate, for example, the nickel salt may be selected from at least one of nickel sulfate, nickel chloride, nickel nitrate, and nickel acetate; the cobalt salt may be at least one selected from the group consisting of cobalt sulfate, cobalt chloride, cobalt nitrate and cobalt acetate; the manganese salt may be selected from at least one of manganese sulfate, manganese chloride, manganese nitrate and manganese acetate.
In some embodiments of the present invention, preferably, in step S1, the nickel salt, the cobalt salt, and the manganese salt are used in amounts such that, in terms of mole of nickel, cobalt, and manganese, n (ni): n (Co): n (Mn) ═ x 1 :y 1 :z 1 。
In some embodiments of the present invention, preferably, the first precipitating agent is selected from sodium hydroxide and/or potassium hydroxide; the first complexing agent is at least one selected from ammonia water, disodium ethylene diamine tetraacetate, ammonium nitrate, ammonium chloride and ammonium sulfate.
In some embodiments of the present invention, the first precipitating agent and the first complexing agent are used in amounts such that the pH of the system is 10 to 13 when the first continuous reaction is performed in step S1.
In some embodiments of the present invention, in step S2, the first lithium salt may be any conventional lithium salt in the art. For example, the first lithium salt may be at least one selected from lithium carbonate, lithium hydroxide, lithium nitrate, and lithium oxide.
In some embodiments of the invention, the first dopant is M-containing 1 Oxides, hydroxides and carbonates of elementsFor example, the first dopant may be selected from TiO 2 、ZrO 2 、Al 2 O 3 、Al(OH) 3 、Nb 2 O 5 、Y 2 O 3 、WO 3 、Ta 2 O 5 、V 2 O 5 、Cr 2 O 3 、MoO 3 、La 2 O 3 、CeO、Er 2 O 3 MgO and B 2 O 3 At least one of (1).
In some embodiments of the present invention, preferably, in step S2, the first dopant M 1 The dosage of the (C) is more than or equal to 0 [ n (M) 1 )]/[n(Ni)+n(Co)+n(Mn)]0.1 or less, more preferably, the first dopant M 1 The dosage of the (C) is more than or equal to 0 [ n (M) 1 )]/[n(Ni)+n(Co)+n(Mn)]≤0.05。
In some embodiments of the invention, the first capping agent comprises J 1 Selected from ZrO 2 、Al 2 O 3 、Al(OH) 3 、TiO 2 、V 2 O 5 、H 3 BO 3 、Co(OH) 2 And WO 3 At least one of (1).
In some embodiments of the invention, in step S3, the first coating agent is used in an amount satisfying 0. ltoreq. n (J) 1 )]/[n(Ni)+n(Co)+n(Mn)]0.02 or less, more preferably, the first coating agent J 1 The dosage of the compound satisfies the condition that n (J) is more than or equal to 0 1 )]/[n(Ni)+n(Co)+n(Mn)]When the surface defect of the particle is not more than 0.015, the residual alkali on the surface of the particle can be consumed while the surface defect of the particle is just repaired, and meanwhile, the phenomenon that the coating amount is too large, the form of the surface of the particle is changed, and the performance of the multielement cathode material is influenced is prevented.
Polycrystalline particle B
According to the invention, the polycrystalline particles B are prepared according to the following steps:
(a) mixing nickel salt, cobalt salt, manganese salt, a second precipitator and a second complexing agent in the presence of a solvent, adding the mixture into a reaction kettle for a second continuous reaction, and performing filter pressing, washing and drying to obtain a precursor of the polycrystalline anode material B;
(b) mixing the precursor of the polycrystalline positive electrode material B with a second lithium salt and a second dopant M 2 Mixing, performing third sintering, crushing and screening to obtain a process product of the polycrystalline anode material B;
(c) the process product of the polycrystalline cathode material B and a second coating agent J 2 Performing fourth sintering to obtain polycrystalline particles B;
wherein M is 2 At least one element selected from Ta, Cr, Mo, W, La, Al, Y, Ti, Zr, V, Nb, Ce, Er, Mg, Sr, Ba and B, J 2 At least one element selected from the group consisting of W, Mo, Zr, Al, V, Ti, B, Co and Nb.
In some embodiments of the invention, the second lithium salt is used in an amount satisfying 0.9 ≦ n (Li)/[ n (Ni) + n (Co) + n (Mn) ] ≦ 1.1, and more preferably, in an amount satisfying 1.01 ≦ n (Li)/[ n (Ni) + n (Co) + n (Mn) ] ≦ 1.08.
In some embodiments of the present invention, in order to obtain a precursor of the polycrystalline cathode material B, preferably, in step (a), the second continuous reaction is performed under reaction conditions including: the temperature is 45-70 ℃, the time is 10-30h, the rotating speed is 300-900rpm, and the pH value is 10.2-13.2.
In the present invention, it is preferable that the pH of the second continuous reaction is higher than the pH of the first continuous reaction.
In the invention, when the pH of the second continuous reaction is controlled to be higher than that of the first continuous reaction, the prepared polycrystalline particle precursor can be compact in structure, and the single crystal particle precursor is loose in structure, so that the single crystal particles and the polycrystalline particles in the first aspect of the invention can be obtained.
Further, the pH of the second continuous reaction is 0.1 to 2 higher than the pH of the first continuous reaction.
In some embodiments of the present invention, it is preferable that the precursor of the polycrystalline positive electrode material B has a median particle diameter D 50 2-6 μm, and specific surface area of 4-20m 2 /g。
In some embodiments of the present invention, preferably, in step (b), the third sintering is performed in an air or oxygen atmosphere, with the conditions including: the temperature is 500-1000 ℃, and the time is 6-30 h.
In some embodiments of the present invention, preferably, in step (c), the fourth sintering is performed in an air or oxygen atmosphere, with the conditions including: the temperature is 200 ℃ and 900 ℃ and the time is 6-30 h.
In some embodiments of the present invention, preferably, in step (a), the nickel salt, the cobalt salt and the manganese salt are each independently selected from at least one of a sulfate, a chloride, a nitrate and an acetate, for example, the nickel salt may be selected from at least one of nickel sulfate, nickel chloride, nickel nitrate and nickel acetate; the cobalt salt may be at least one selected from the group consisting of cobalt sulfate, cobalt chloride, cobalt nitrate and cobalt acetate; the manganese salt may be selected from at least one of manganese sulfate, manganese chloride, manganese nitrate and manganese acetate.
In some embodiments of the present invention, preferably, in step S1, the nickel salt, the cobalt salt, and the manganese salt are used in amounts such that, in terms of mole of nickel, cobalt, and manganese, n (ni): n (Co) n (Mn) x 2 :y 2 :z 2 。
In some embodiments of the present invention, preferably, the second precipitating agent is selected from sodium hydroxide and/or potassium hydroxide; the second complexing agent is at least one selected from ammonia water, ethylene diamine tetraacetic acid, ammonium nitrate, ammonium chloride and ammonium sulfate.
In some embodiments of the present invention, the second precipitating agent and the second complexing agent are used in amounts such that the pH of the system is from 10.2 to 13.2 when the second continuous reaction is performed in step (a).
In some embodiments of the present invention, in the step (b), the second lithium salt may be various lithium salts conventional in the art, for example, the second lithium salt may be selected from at least one of lithium carbonate, lithium hydroxide, lithium nitrate and lithium oxide.
In some embodiments of the invention, the second dopant is M-containing 2 At least one of an oxide, hydroxide and carbonate of an element, for example the first dopant may be selected from TiO 2 、ZrO 2 、Al 2 O 3 、AlPO 4 、AlCl 3 、Nb 2 O 5 、Y 2 O 3 、WO 3 、Ta 2 O 5 、V 2 O 5 、Cr 2 O 3 、MoO 3 、La 2 O 3 、CeO、Er 2 O 3 MgO, and B 2 O 3 At least one of (a).
In some embodiments of the present invention, preferably, in step (b), the first dopant M 2 The dosage of the (C) is more than or equal to 0 [ n (M) 2 )]/[n(Ni)+n(Co)+n(Mn)]0.1 or less, more preferably, the first dopant M 2 The dosage of (A) satisfies 0 to [ n (M) ] M 2 )]/[n(Ni)+n(Co)+n(Mn)]≤0.05。
In some embodiments of the invention, the second capping agent comprises J 2 Selected from ZrO 2 、Al 2 O 3 、Al(OH) 3 、V 2 O 5 、TiO 2 、H 3 BO 3 、Co(OH) 2 And WO 3 At least one of (1).
In some embodiments of the invention, in step (c), the second coating agent J 2 The dosage of the compound satisfies the condition that n (J) is more than or equal to 0 2 )]/[n(Ni)+n(Co)+n(Mn)]0.02. ltoreq. preferably, the second coating agent J 2 The dosage of the (B) satisfies 0 to [ n (J) 2 )]/[n(Ni)+n(Co)+n(Mn)]Less than or equal to 0.015, can ensure that the covering agent is satisfied when just repairing the surface defect of granule, consume the residual alkali volume on some surfaces, meanwhile, prevent that the cladding volume is too big, change the form on granule surface, influence the performance of many units cathode material.
In some embodiments of the present invention, the single crystal positive electrode material a and the polycrystalline positive electrode material B are prepared by controlling the amount of raw materials, the synthesis temperature, the stirring speed, the pH, the lithium ratio, the sintering temperature, the sintering time, and other conditions.
In some embodiments of the present invention, preferably, the method for preparing the single crystal particles a and the polycrystalline particles B further includes pumping filtration, washing, drying, crushing, sieving, and other post-treatment means known in the art, which will not be described herein again, and those skilled in the art should not be construed as limiting the present invention.
The invention also provides a preparation method of the multi-element cathode material.
The present invention will be described in detail below by way of examples.
In the following examples, all the raw materials were commercially available unless otherwise specified.
The room temperature in the present invention means 25. + -. 2 ℃ unless otherwise specified.
In the following examples and comparative examples, relevant parameters were measured by the following methods:
(1) and (3) morphology testing: obtained by a scanning electron microscope test of a model S-4800 of Hitachi corporation, Hitachi, Japan;
(2) median particle diameter D 50 : obtained by testing with a laser particle analyzer of the type Hydro 2000mu of Marvern company;
(3) specific surface test: obtained by means of a specific surface tester model Tristar 3020 from Micromeritics;
(4) compacting density: the test result is obtained by a tap density tester of BT-30 model of Baite company;
(5) and (3) electrochemical performance testing:
in the following examples and comparative examples, electrochemical performance of the multi-component positive electrode material was tested using 2025 button cell batteries.
The preparation process of the 2025 button cell is as follows:
preparing a pole piece: mixing a multi-element cathode material, acetylene black and polyvinylidene fluoride (PVDF) according to the weight ratio of 95: 3: 2 and a proper amount of N-methylpyrrolidone (NMP) are fully mixed to form uniform slurry, the slurry is coated on an aluminum foil and dried at 120 ℃ for 12 hours, and then the aluminum foil is subjected to punch forming under the pressure of 100MPa to prepare a positive pole piece with the diameter of 12mm and the thickness of 120 mu m, wherein the loading capacity of the multi-element positive pole material is 15-16mg/cm 2 。
Assembling the battery: argon-filled gas hand with water content and oxygen content less than 5ppmAnd in the case, assembling the positive pole piece, the diaphragm, the negative pole piece and the electrolyte into the 2025 type button cell, and standing for 6 hours. Wherein, the negative pole piece uses a metal lithium piece with the diameter of 17mm and the thickness of 1 mm; the separator used was a polyethylene porous membrane (Celgard 2325) having a thickness of 25 μm; LiPF (1 mol/L) was used as an electrolyte 6 And a mixture of Ethylene Carbonate (EC) and diethyl carbonate (DEC) in equal amounts.
And (3) electrochemical performance testing:
in the following examples and comparative examples, electrochemical performance of 2025 type button cell was tested by Shenzhen New Willebell test system, and the charge and discharge current density at 0.1C was 200 mA/g.
And controlling the charging and discharging voltage interval to be 3.0-4.3V, and carrying out charging and discharging tests on the button cell at room temperature under 0.1C to evaluate the first charging and discharging specific capacity and the first charging and discharging efficiency of the multi-element anode material.
And (3) testing cycle performance: controlling the charging and discharging voltage interval to be 3.0-4.3V, and carrying out charging and discharging circulation on the button cell for 2 times at the constant temperature of 45 ℃ at 0.1 ℃, and then carrying out charging and discharging circulation for 80 times at 1 ℃ to evaluate the high-temperature capacity retention rate of the multi-element anode material.
And (3) rate performance test: controlling the charging and discharging voltage interval to be 3.0-4.3V, at room temperature, performing charging and discharging circulation on the button cell for 2 times at 0.1C, then performing charging and discharging circulation for 1 time at 0.2C, 0.33C, 0.5C and 1C respectively, and evaluating the rate capability of the multielement anode material by the ratio of the first discharging specific capacity at 0.1C to the discharging specific capacity at 1C. Wherein, the first discharge specific capacity of 0.1C is the discharge specific capacity of the button cell in the 1 st cycle, and the 1C discharge specific capacity is the discharge specific capacity of the button cell in the 6 th cycle.
Preparation A1
S1: nickel sulfate, cobalt sulfate and manganese sulfate are mixed according to the molar ratio of nickel, cobalt and manganese elements as 82: 10: 8 to obtain a mixed salt solution with the concentration of 2 mol/L; dissolving sodium hydroxide into a precipitant solution with the concentration of 8 mol/L; dissolving ammonia water into a complexing agent solution with the concentration of 5.2 mol/L. Introducing 100L of mixed salt solution, precipitator solution and complexing agent solution into a reaction kettle in a parallel flow mode, carrying out first continuous reaction for 20h under the conditions of temperature of 60 ℃, pH of 11.38 and stirring speed of 600rpm, then carrying out suction filtration and washing on precursor slurry under the protection of nitrogen atmosphere, drying a filter cake at 115 ℃ and then screening to obtain a precursor of a single crystal anode material A1;
s2: the precursor of the single crystal anode material A prepared by S1 is mixed with LiOH and ZrO 2 And SrCO 3 According to the formula of Li/(Ni + Co + Mn)/Zr/Sr, 1.05: 1: 0.003: heating to 830 ℃ from room temperature in an oxygen atmosphere at a molar ratio of 0.002, preserving heat for 18 hours for primary sintering, and cooling, crushing and screening to obtain a process product A of the single crystal anode material;
s3 preparation of the single crystal anode material A process product prepared by the S2 and a coating agent V 2 O 5 Heating the mixture from room temperature to 750 ℃ in an air atmosphere according to the molar ratio of (Ni + Co + Mn)/V being 1:0.002, preserving the heat for 10 hours for secondary sintering, cooling, crushing and screening to obtain the single crystal particles A1. The composition and structural parameters of the single crystal particle a1 are shown in tables 2 and 3, respectively.
Scanning electron microscope images (SEM) of the precursor of the single crystal cathode material a1, the single crystal particles a1 are shown in fig. 1 and fig. 3. As can be seen from fig. 1 and fig. 3, the surface of the precursor of the single crystal positive electrode material a1 is looser, the single crystal particles a1 have better single crystallization degree, and the surface is smooth and round.
Preparation examples A2-A5 and comparative preparation example DA1
The process of preparation A1 is followed except that: the single crystal particles A2-A3 were prepared by using the same process as in preparation A1 except that the recipe and process parameters used were different as shown in Table 1. The compositions and structural parameters of the single crystal particles A2-A5 and the single crystal particles DA1 are shown in tables 2 and 3, respectively.
TABLE 1
TABLE 2
TABLE 3
| D 50(A) (μm) | S A (m 2 /g) | |
| Preparation A1 | 3.56 | 0.62 |
| Preparation example A2 | 4.21 | 0.65 |
| Preparation A3 | 3.32 | 0.69 |
| Preparation example A4 | 5.71 | 0.51 |
| Preparation A5 | 2.64 | 0.97 |
| Comparative preparation DA1 | 1.64 | 0.83 |
Preparation example B1
S1: nickel sulfate, cobalt sulfate and manganese sulfate are mixed according to the molar ratio of nickel, cobalt and manganese elements of 80: 10: dissolving according to the proportion of 10 to obtain a mixed salt solution with the concentration of 2 mol/L; dissolving sodium hydroxide into a precipitant solution with the concentration of 8 mol/L; dissolving ammonia water into a complexing agent solution with the concentration of 5.2 mol/L. Introducing 100L of mixed salt solution, precipitator solution and complexing agent solution into a reaction kettle in a parallel flow mode, carrying out second continuous reaction for 16h under the conditions of temperature of 60 ℃, pH of 11.60 and stirring speed of 600rpm, then carrying out suction filtration and washing on precursor slurry under the nitrogen protection atmosphere, drying a filter cake at 115 ℃ and then screening to obtain a precursor of the polycrystalline anode material B1;
s2: precursor of polycrystalline positive electrode material B prepared by S1, LiOH and ZrO 2 And SrCO 3 According to the formula of Li/(Ni + Co + Mn)/Zr/Sr, 1.05: 1: 0.002: heating to 800 ℃ from room temperature in an oxygen atmosphere at a molar ratio of 0.001, preserving heat for 14 hours, performing third sintering, cooling, crushing and screening to obtain a polycrystalline cathode material B process product;
s3 preparation of polycrystalline cathode material B process product prepared from S2 and coating agent V 2 O 5 Heating the mixture from room temperature to 720 ℃ in an air atmosphere according to the molar ratio of (Ni + Co + Mn)/V being 1:0.002, preserving the heat for 10 hours, carrying out fourth sintering, cooling, crushing and screening to obtain polycrystalline particles B1. The composition and structural parameters of polycrystalline grain B1 are shown in tables 5 and 6, respectively.
Scanning electron microscope images (SEM) of a precursor of polycrystalline positive electrode material B1, polycrystalline grain B1, are shown in fig. 2 and 4. As can be seen from fig. 2 and 4, the precursor of the polycrystalline positive electrode material B1 has a large and round grain structure and a dense grain surface, compared to the precursor of the single-crystal positive electrode material a 1. The polycrystalline grain B1 was more uniform and uniform in grain size than the single-crystal grain A1.
Preparation examples B2-B5 and comparative preparation example DB1
Preparations B2-B3 were prepared according to the procedure of preparation B1, except that the formulations and process parameters used were different, as shown in Table 4, and the rest were the same as in preparation B1. The compositions and structural parameters of polycrystalline grains B2-B5 and polycrystalline grain DB1 are shown in tables 5 and 6, respectively.
TABLE 4
TABLE 5
| Composition of polycrystalline particles B | |
| Preparation B1 | Li 1.05 Ni 0.80 Co 0.10 Mn 0.10 Zr 0.002 Sr 0.001 V 0.002 O 2 |
| Preparation B2 | Li 1.04 Ni 0.60 Co 0.20 Mn 0.20 Y 0.002 Ba 0.002 Al 0.001 O 2 |
| Preparation example B3 | Li 1.06 Ni 0.90 Co 0.05 Mn 0.05 Al 0.0025 Ta 0.0025 B 0.003 O 2 |
| Preparation B4 | Li 1.05 Ni 0.80 Co 0.10 Mn 0.10 Zr 0.002 Sr 0.001 V 0.002 O 2 |
| Preparation B5 | Li 1.05 Ni 0.80 Co 0.10 Mn 0.10 Zr 0.002 Sr 0.001 V 0.002 O 2 |
| Comparative preparation example DB1 | Li 1.05 Ni 0.80 Co 0.10 Mn 0.10 Zr 0.002 Sr 0.001 V 0.002 O 2 |
TABLE 6
| D 50(B) (μm) | S B (m 2 /g) | |
| Preparation B1 | 3.62 | 1.35 |
| Preparation B2 | 4.15 | 1.38 |
| Preparation B3 | 3.25 | 1.47 |
| Preparation example B4 | 5.77 | 1.26 |
| Preparation B5 | 2.12 | 1.54 |
| Comparative preparation example DB1 | 13.54 | 1.09 |
Example 1
The single-crystal grain a1 produced in production example a1 and the polycrystalline grain B1 produced in production example B1 were mixed in the following ratio of 7: 3 to obtain a multi-element cathode material P1. The structural parameters of the multi-element positive electrode material are shown in table 8.
Fig. 5 shows a Scanning Electron Microscope (SEM) image of the multi-component positive electrode material P1. As can be seen from fig. 5, in the multi-component cathode material P1, the single crystal grains a1 and the polycrystalline grains B1 are blended, so that the polycrystalline material and the single crystal material in the multi-component cathode material P1 can be uniformly distributed.
Examples 2 to 12 and comparative examples 1 to 4
The process of example 1 was followed except that: the specific types of the single crystal grains and the polycrystalline grains, and the blending ratios of the single crystal grains and the polycrystalline grains were different, and are specifically shown in table 7. The multi-element cathode materials P2-P12 and DP1-DP5 are obtained, and the structural parameters and the compaction density of the multi-element cathode materials are tested, and the results are shown in Table 8. And fracturing the multi-element positive electrode material at the pressure of 4.5T. The specific surface area of the multi-element cathode material before and after 4.5T pressure is S 0 、S 1 And D of the positive electrode material before and after 4.5T pressure 5 0 、D 5 1 The specific test results are shown in table 9.
TABLE 7
| Single crystal particle | Polycrystalline particles | A/B | ∣D 50 (A)-D 50 (B)∣ | x 1 -x 2 | |
| Example 1 | A1 | B1 | 7：3 | 0.06 | 0.02 |
| Example 2 | A1 | B1 | 5：5 | 0.06 | 0.02 |
| Example 3 | A1 | B1 | 3：7 | 0.06 | 0.02 |
| Example 4 | A1 | B1 | 9：1 | 0.06 | 0.02 |
| Example 5 | A1 | B1 | 1：9 | 0.06 | 0.02 |
| Example 6 | A2 | B2 | 7：3 | 0.06 | 0.02 |
| Example 7 | A3 | B3 | 7：3 | 0.07 | 0.02 |
| Example 8 | A5 | B1 | 7：3 | 0.98 | 0.02 |
| Example 9 | A5 | B4 | 7：3 | 1.51 | 0.02 |
| Example 10 | A4 | B5 | 7：3 | 3.59 | 0.02 |
| Example 11 | A3 | B1 | 7：3 | 0.30 | 0.12 |
| Example 12 | A2 | B1 | 7：3 | 0.59 | -0.18 |
| Comparative example 1 | A1 | / | 1：0 | / | / |
| Comparative example 2 | / | B1 | 0：1 | / | / |
| Comparative example 3 | A1 | DB1 | 7：3 | 9.98 | 0.02 |
| Comparative example 4 | DA1 | B1 | 7：3 | 1.98 | 0.02 |
| Comparative example 5 | A1 | B1 | 9.8：0.2 | 0.06 | 0.02 |
TABLE 8
From the results in table 8, it can be seen that the powder compacted density and the pole piece compacted density of the blended multi-component positive electrode material are both greater than those of the single crystal material and the polycrystalline material, and the compacted density of the blended material increases with the increase of the single crystal material; and the more the amount of the single crystal particles used, the median diameter D 50 The greater the compaction density of the multi-element positive electrode material.
TABLE 9
As can be seen from the results in Table 9, the specific surface area of the blended multi-component positive electrode material after 4.5T pressure fracturing increases with increasing B content of the polycrystalline positive electrode material, and D 5 The smaller the size, the more the multi-element material is cracked after being pressed; the more the single crystal positive electrode material A is, the specific surface area and D 5 The smaller the change is, the single crystal material can improve the compaction strength of the anode material, so that the material is not easy to crack. And D of single crystal particles 50 Is not easy to be fractured; if the polycrystalline particles D 50 Relatively single crystal particle D 50 Large, it is easily fractured, and D 50 The larger the difference, the more susceptible to fracturing.
Test example
The electrochemical properties of the multi-element cathode material prepared in the above examples and comparative examples, including the 0.1C first discharge specific capacity, 1C discharge specific capacity, cycle performance and rate capability, were tested, and the specific test results are shown in table 10.
As can be seen from the results of table 10, when the multi-element positive electrode material prepared in comparative example 1 using single crystal particles alone was used to assemble a battery, the cycle performance of the battery was good, but the rate performance was poor; when the multi-element cathode material prepared in comparative example 2, in which polycrystalline particles are used alone, is used for assembling a battery, the rate performance of the battery is good, but the cycle performance is poor.
The multi-element cathode material provided by the embodiments 1 to 5 has a high content of the single crystal particles a, so that the battery comprising the multi-element cathode material has a better cycle performance, and the rate performance of the battery can be obviously improved by adding the polycrystalline particles B; the content of the polycrystalline particles B is high, the rate performance of the battery is better, and the cycle performance of the material can be improved by adding the monocrystalline particles A; the two mixed materials can not only keep the better cycle performance of the single crystal material, but also have the better rate performance of the polycrystalline material.
In the multi-element cathode materials provided in examples 8 to 9, the single crystal particles have a small median particle size, and thus the rate capability is slightly good, but the cycle performance is poor; example 9 provides a multi-element positive electrode material in which the median particle diameter of polycrystalline particles is large, the median particle diameter of single crystal particles is small, and D 50 The difference is large, so that the rate performance and the cycle performance of the battery containing the multi-element cathode material are poorer than those of the battery in example 1.
In the multi-element cathode material provided in example 10, the median diameter of the single crystal particles is large, and the median diameter of the polycrystalline particles is small, so that the discharge capacity of the battery assembled by the multi-element cathode material is low, and the rate capability is poor.
The difference between the nickel contents of the single crystal particles and the polycrystalline particles in the multi-element cathode material provided in example 11 is large, and the capacity mismatch between the single crystal particles and the polycrystalline particles is caused by the fact that the nickel content of the single crystal particles is lower than that of the polycrystalline particles in the multi-element cathode material provided in example 12.
In the multi-element cathode material provided by comparative example 3, the median diameter of the polycrystalline particles is too large, so that the multi-element cathode material is easily crushed, and finally, the capacity and the rate of the battery assembled by the multi-element cathode material are poor.
In the multi-element cathode material provided by comparative example 4, the median diameter of the single crystal particles is too small to play a supporting role, so that the multi-element cathode material is easily crushed, and finally, the cycle retention rate of the battery assembled by the multi-element cathode material is poor.
In the multi-element cathode material provided by comparative example 5, the use amount of polycrystalline particles is small, so that the effect of improving the battery rate cannot be achieved.
As shown in fig. 6, the results of the high-temperature cycle performance test of the multi-element cathode materials prepared in example 1 and comparative examples 1 and 2 show that the multi-element cathode material of the present invention has high cycle capacity retention rate and good cycle performance, and compared with the multi-element cathode materials prepared in comparative examples 1 and 2, the multi-element cathode material of the present invention has both capacity retention rate and cycle stability, and the embodiment 1 has higher compaction density and more excellent pressure resistance.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including various technical features being combined in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. A multi-element cathode material is characterized in that the multi-element cathode material comprises single crystal particles A and polycrystalline particles B;
wherein the single crystal particles A have a median particle diameter D 50(A) Is 2-6 μm; the median diameter D of the polycrystalline particles B 50(B) 2-6 μm;
the weight ratio of the single crystal grains A to the polycrystalline grains B is 1:9-9: 1.
2. The multi-element positive electrode material according to claim 1, wherein the single-crystal particles A areMedian particle diameter D 50(A) Is 3-5 μm;
preferably, the median particle diameter D of the polycrystalline particles B 50(B) Is 3-5 μm;
preferably, the weight ratio of the single crystal grains a to the polycrystalline grains B is 2:8 to 8: 2;
preferably, the median particle diameter D of the multi-component positive electrode material 50 Is 2 to 6 μm, more preferably 3 to 5 μm.
3. The multi-element positive electrode material according to claim 1 or 2, wherein the single crystal particles a have a median particle diameter D 50(A) And a median diameter D of the polycrystalline particles B 50(B) The absolute value of the difference is 1 μm or less, preferably 0.8 μm or less;
preferably, the specific surface area S of the single-crystal particles A A Is 0.4-1m 2 A/g, preferably of 0.5 to 0.9m 2 /g；
Preferably, the specific surface area S of the polycrystalline particles B B Is 0.9-2m 2 A/g, preferably 1.1 to 1.6m 2 /g。
4. The multielement positive electrode material according to any one of claims 1 to 3, wherein the single crystal particles A have a composition as shown in formula I:
Li 1+a1 (Ni x1 Co y1 Mn z1 M 1m1 )J 1j1 O 2 formula I;
wherein-0.1. ltoreq. a 1 ≤0.1，0＜x 1 ＜1，0＜y 1 ≤0.4，0＜z 1 ≤0.6，0≤m 1 ≤0.1，0≤j 1 ≤0.02；M 1 At least one element selected from Ta, Cr, Mo, W, La, Al, Y, Ti, Zr, V, Nb, Ce, Er, Mg, Sr, Ba and B; j. the design is a square 1 At least one element selected from W, Mo, Zr, Al, V, Ti, B, Co and Nb;
preferably, the polycrystalline particles B have a composition represented by formula II:
Li 1+a2 (Ni x2 Co y2 Mn z2 M 2m2 )J 2j2 O 2 formula II;
wherein-0.1. ltoreq. a 2 ≤0.1，0＜x 2 ＜1，0＜y 2 ≤0.4，0＜z 2 ≤0.6，0≤m 2 ≤0.1，0≤j 2 ≤0.02；M 2 At least one element selected from Ta, Cr, Mo, W, La, Al, Y, Ti, Zr, V, Nb, Ce, Er, Mg, Sr, Ba and B; j. the design is a square 2 At least one element selected from W, Mo, Zr, Al, V, Ti, B, Co and Nb;
preferably, x 1 ＞x 2 More preferably, x 1 -x 2 Is 0.01-0.1.
5. The multi-element positive electrode material according to any one of claims 1 to 4, wherein the multi-element positive electrode material has a specific surface area S 0 After 4.5T of pressure fracturing, the specific surface area of the multielement positive electrode material is S 1 ；
Wherein (S) 1 -S 0 )/S 0 100% to 200%, preferably 10-150%.
6. The multi-element positive electrode material according to any one of claims 1 to 5, wherein the multi-element positive electrode material has a particle size D corresponding to 5% of a volume distribution obtained by a particle size test 5 0 After 4.5T pressure fracturing, the granularity D corresponding to 5% of volume distribution obtained by granularity test of the multi-element anode material 5 1 ；
Wherein (D) 5 0 -D 5 1 )/D 5 0 X 100% is 1 to 30%, preferably 1 to 25%.
7. The multi-element positive electrode material according to any one of claims 1 to 6, wherein the weight ratio of the single crystal particles A to the polycrystalline particles B is 1.1 to 9:1, the multielement cathode material satisfies at least one of the following conditions:
(i)0.5≤S 0 ≤1.2m 2 /g, preferably 0.5. ltoreq.S 0 ≤1m 2 /g；
(ii)(S 1 -S 0 )/S 0 X is 100 percent to 120 percent, preferably 10 to 100 percent;
(iii)(D 5 0 -D 5 1 )/D 5 0 x 100% is 1-15%, preferably 1-10%;
(iv)0≤(S 0 -S A )/S A x is 100 percent to 50 percent, preferably 0 to 30 percent;
wherein S is A Is the specific surface area of the single crystal particle A.
8. The multi-element positive electrode material according to any one of claims 1 to 6, wherein when a weight ratio of the single crystal grains A to the polycrystalline grains B satisfies 1:1.1 to 9,
the multielement cathode material meets at least one of the following conditions:
(1)0.8≤S 0 ≤1.4m 2 /g, preferably 1. ltoreq. S 0 ≤1.3m 2 /g；
(ii)(S 1 -S 0 )/S 0 X is 100 percent to 200 percent, preferably 90 to 180 percent;
(iii)(D 5 0 -D 5 1 )/D 5 0 x 100% is 10-30%, preferably 10-25%;
(iv)0≤(S B -S 0 )/S B x 100% to 50%, preferably 0 to (S) B -S 0 )/S B ×100％≤30％；
Wherein S is B Is the specific surface area of the polycrystalline particles B.
9. A method for producing a multi-element positive electrode material according to any one of claims 1 to 8, characterized in that the method comprises:
mixing the single crystal particles A with the polycrystalline particles B to obtain the multi-element anode material;
preferably, the single crystal particle a is prepared according to the following steps:
s1, mixing nickel salt, cobalt salt, manganese salt, a first precipitator and a first complexing agent in the presence of a solvent, adding the mixture into a reaction kettle to perform a first continuous reaction, and performing filter pressing, washing and drying to obtain a precursor of the single crystal anode material A;
s2, mixing the precursor of the single crystal anode material A with a first lithium salt and a first doping agent M 1 Mixing, and performing first sintering, crushing and screening to obtain a process product of the single crystal cathode material A;
s3, mixing the single crystal anode material A process product with a first coating agent J 1 Performing second sintering to obtain the single crystal particles A;
wherein, M 1 At least one element selected from Ta, Cr, Mo, W, La, Al, Y, Ti, Zr, V, Nb, Ce, Er, Mg, Sr, Ba and B, J 1 At least one element selected from W, Mo, Zr, Al, V, Ti, B, Co and Nb;
preferably, the polycrystalline particles B are prepared according to the following steps:
(a) mixing nickel salt, cobalt salt, manganese salt, a second precipitator and a second complexing agent in the presence of a solvent, adding the mixture into a reaction kettle to perform a second continuous reaction, and performing filter pressing, washing and drying to obtain a precursor of a polycrystalline anode material B;
(b) mixing the precursor of the polycrystalline positive electrode material B with a second lithium salt and a second doping agent M 2 Mixing, sintering for the third time, crushing and screening to obtain a process product of the polycrystalline positive electrode material B;
(c) the process product of the polycrystalline cathode material B and a second coating agent J 2 Performing fourth sintering to obtain polycrystalline particles B;
wherein M is 2 At least one element selected from Ta, Cr, Mo, W, La, Al, Y, Ti, Zr, V, Nb, Ce, Er, Mg, Sr, Ba and B, J 2 At least one element selected from W, Mo, Zr, Al, V, Ti, B, Co and Nb.
10. Use of the multi-element positive electrode material of any one of claims 1 to 8 in a lithium ion battery.
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| CN113921782A (en) * | 2021-09-26 | 2022-01-11 | 宁波容百新能源科技股份有限公司 | Ultrahigh nickel ternary cathode material with high compaction and high energy density |
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